CN109590006B - Preparation method of triazine/heptazine homone heterojunction carbon nitride photocatalyst - Google Patents
Preparation method of triazine/heptazine homone heterojunction carbon nitride photocatalyst Download PDFInfo
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- CN109590006B CN109590006B CN201811539287.XA CN201811539287A CN109590006B CN 109590006 B CN109590006 B CN 109590006B CN 201811539287 A CN201811539287 A CN 201811539287A CN 109590006 B CN109590006 B CN 109590006B
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- heptazine
- carbon nitride
- melamine
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 53
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 title claims abstract description 51
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 51
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 51
- YSRVJVDFHZYRPA-UHFFFAOYSA-N melem Chemical compound NC1=NC(N23)=NC(N)=NC2=NC(N)=NC3=N1 YSRVJVDFHZYRPA-UHFFFAOYSA-N 0.000 claims abstract description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 230000001699 photocatalysis Effects 0.000 claims abstract description 15
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 58
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 58
- 239000000203 mixture Substances 0.000 claims description 34
- 235000011164 potassium chloride Nutrition 0.000 claims description 29
- 239000001103 potassium chloride Substances 0.000 claims description 29
- 239000000919 ceramic Substances 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000006104 solid solution Substances 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 239000012300 argon atmosphere Substances 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- 239000012528 membrane Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 35
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 239000000969 carrier Substances 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 4
- 238000005215 recombination Methods 0.000 abstract description 4
- 230000006798 recombination Effects 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 4
- 239000013535 sea water Substances 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 9
- 239000004570 mortar (masonry) Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 230000000630 rising effect Effects 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- HCITUYXHCZGFEO-UHFFFAOYSA-N 1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.N=C1NC(=N)NC(=N)N1 HCITUYXHCZGFEO-UHFFFAOYSA-N 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention relates to a photocatalytic material, in particular to a preparation method of a triazine/heptazine homone heterojunction carbon nitride photocatalyst, belonging to the technical field of preparation of photocatalytic materials. The invention can produce the triazine/heptazine allotrope heterojunction carbon nitride photocatalyst capable of efficiently decomposing seawater to produce hydrogen by photocatalysis in batches only by calcining the adduct of melamine and melem in the molten salt without adopting high temperature and high pressure, and effectively solves the problem of the prior block g-C3N4The material has the defects of poor conductivity and high recombination rate of photon-generated carriers, so that the photocatalytic hydrogen production performance and the quantum efficiency are remarkably improved.
Description
Technical Field
The invention relates to a photocatalytic material, in particular to a preparation method of a triazine/heptazine homone heterojunction carbon nitride photocatalyst, belonging to the technical field of preparation of photocatalytic materials.
Background
CO in the earth's atmosphere due to the current human over-exploitation and consumption of fossil fuels2The content of (a) is continuously increasing, causing an increasingly severe greenhouse effect. Therefore, the development of energy carriers capable of replacing fossil fuels is urgent. Among various new energy sources, hydrogen energy is the best choice. However, the current production of hydrogen is still dependent on the consumption of fossil fuels, which does not reduce CO2And (4) discharging. In recent years, a new photocatalytic water splitting hydrogen production technology is a technical means for directly splitting water into hydrogen and oxygen by using sunlight as a driving source, and CO can be obtained2Zero emission becomes the hotspot of the current research.
Graphite phase carbon nitride (g-C)3N4) The photocatalyst is an emerging organic semiconductor photocatalyst which can utilize sunlight to decompose water into hydrogen and oxygen in recent years. The material toolHas the characteristics of stable physical and chemical properties, abundant and easily obtained preparation raw materials, and capability of decomposing water to produce hydrogen and oxygen under the irradiation of visible light. But blocks g-C prepared by conventional means3N4The method has the defects of poor conductivity, high recombination rate of photon-generated carriers, low photocatalytic hydrogen production efficiency and the like. By the pair g-C3N4Regulation of internal molecular structure to prepare novel g-C with triazine/heptazine homone heterojunction structure3N4The material can build a built-in electric field in the material, thereby greatly reducing the recombination rate of carriers and further improving the hydrogen production performance of photocatalytic water decomposition. However, the g-C of such triazine/heptazine homojunction heterostructures are currently prepared3N4The material is prepared by apparently mixing melamine and melem and then carrying out polycondensation in molten salt, and the novel g-C of the triazine/heptazine homojunction heterojunction structure prepared by the method3N4The material is not homogeneous composite, a heterojunction is only constructed on the surface of the material, the interior of the material still presents a non-electric field driving state, and the performance of the prepared photocatalyst is not high. Therefore, the g-C which is simple to explore and can be used for homogeneously compounding triazine/heptazine homoheterojunction3N4The material becomes a hot spot and a focus in the research field of the carbon nitride material at present.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the triazine/heptazine homone heterojunction carbon nitride photocatalyst which is simple to operate, green in synthetic process, free from high temperature and high pressure and capable of realizing batch production by only calcining the melamine and melem adduct in molten salt and efficiently decomposing seawater to produce hydrogen through photocatalysis, and effectively solves the problem of the existing block g-C3N4The material has the defects of poor conductivity and high recombination rate of photon-generated carriers, so that the photocatalytic hydrogen production performance and the quantum efficiency are remarkably improved.
In order to realize the purpose of the invention, the concrete steps are as follows:
(1) preparation of melamine and melem adducts: weighing melamine, placing the melamine in a ceramic crucible, and covering a crucible cover; then placing the crucible in a tube furnace, under the protection of high-purity argon, raising the temperature to a certain temperature at a certain heating rate program, keeping the temperature for a period of time, and naturally cooling the crucible to room temperature to obtain a white melamine and melem adduct;
(2) uniformly grinding the mixture of the melamine and miller amine adduct obtained in the step (1) and lithium chloride and potassium chloride in a glove box under the protection of nitrogen, pouring the mixture into a ceramic crucible, and covering the ceramic crucible with a cover;
(3) and (3) placing the ceramic crucible in a tube furnace, heating to a certain temperature at a certain heating rate under the protection of argon atmosphere, keeping for a period of time, and naturally cooling to room temperature to obtain the solid solution of triazine/heptazine allotrope heterojunction carbon nitride, lithium chloride and potassium chloride.
(4) And (4) dispersing the solid solution obtained in the step (3) by using boiling water, and filtering and washing the solid solution by using a filter membrane with the diameter of 0.22 mu m to obtain the triazine/heptazine allotrope heterojunction carbon nitride photocatalyst.
Preferably, the temperature rise rate in the step (1) is 2-10 ℃/min.
Preferably, the temperature raising in the step (1) is 360-430 ℃, and the holding time is 4-24 h.
Preferably, the flow rate of the argon in the step (1) is 50-400 mL/min.
Preferably, the mass ratio of the adduct of melamine and melem to the mixture of lithium chloride and potassium chloride in the step (2) is 1:30-1: 6; in the mixture of lithium chloride and potassium chloride, the mass ratio of lithium chloride to potassium chloride is 9: 11.
Preferably, the heating rate in the step (3) is 10-20 ℃/min.
Preferably, the temperature raising in the step (3) is 550-600 ℃, and the holding time is 4-6 h.
Preferably, the flow rate of the argon in the step (3) is 50-400 mL/min.
Preferably, the boiling water in the step (4) is deionized water with the temperature of 100 ℃ under the standard atmospheric pressure, and the washing times are 6-20 times.
Has the advantages that:
compared with the prior art for synthesizing carbon nitride, the method has the following obvious advantages: the preparation process is simple and easy to operate, and the triazine/heptazine homone heterojunction carbon nitride photocatalyst material capable of efficiently decomposing seawater to produce hydrogen can be obtained by a mode of polycondensing an adduct of melamine and melem in molten salt. The triazine/heptazine allotrope heterojunction carbon nitride photocatalyst material prepared by the method shows very high performance of hydrogen production by photocatalytic decomposition of water, the hydrogen activity of the water by photocatalytic decomposition under visible light irradiation can reach 32885 mu mol/gh, and the quantum efficiency can reach 57%. The activity of the catalyst is 70 times that of carbon nitride prepared by the conventional process. The method has the advantages of simple process, good reproducibility, cheap and easily-obtained raw materials and convenience for batch production.
Drawings
FIG. 1 shows the blocks g-C thus prepared3N4And XRD spectrograms of triazine/heptazine allotrope heterojunction carbon nitride samples obtained at different temperatures.
FIG. 2 SEM image of the triazine/heptazine homone heterojunction carbon nitride prepared.
FIG. 3 is a ultraviolet-visible light diffuse reflectance absorption (DRS) spectrum of the prepared sample.
FIG. 4 shows g-C under irradiation of visible light3N4And a schematic diagram of the hydrogen production activity of the synthesized triazine/heptazine homone heterojunction carbon nitride photocatalyst.
Detailed Description
The following are examples of the present invention to further illustrate the invention, but the scope of the invention is not limited thereto.
Example 1
The preparation of the adduct of melamine and melem is carried out as follows: 1.0g of melamine was weighed into a 20mL ceramic crucible and the crucible lid was covered. Then the crucible is placed in a tube furnace, the temperature is programmed to 370 ℃ at the heating rate of 2 ℃/min under the argon atmosphere with the flow rate of 100mL/min, the mixture is kept for 4h and then is naturally cooled to the room temperature to prepare the white melamine and melem adduct. 0.2g of the calcined adduct material of melamine and melem was then weighed out into an agate mortar in a glove box under nitrogen and mixed with 2.7g of lithium chloride and 3.3g of potassium chloride before intensive grinding. The milled mixture was then poured into a ceramic crucible and the lid was closed. And then, putting the crucible filled with the mixture into a tubular furnace again, carrying out temperature programming to 550 ℃ at the temperature rising rate of 10 ℃/min under the argon atmosphere with the flow rate of 50mL/min, keeping for 4h, and naturally cooling to room temperature to prepare the solid solution of the triazine/heptazine allotrope heterojunction carbon nitride, the lithium chloride and the potassium chloride. Then dispersing the obtained solid solution into deionized water at 100 ℃ under the standard atmospheric pressure, filtering and washing by using a filter membrane with the diameter of 0.22 mu m after full dispersion, and repeating the washing process for 6 times. Finally, the obtained solid is collected and dried at the temperature of 60 ℃ to obtain the triazine/heptazine allotrope heterojunction carbon nitride photocatalyst material.
Example 2
The preparation of the adduct of melamine and melem is carried out as follows: 4.0g of melamine was weighed into an 80mL ceramic crucible and the crucible lid was covered. And then placing the crucible into a tube furnace, raising the temperature to 390 ℃ in an argon atmosphere with the flow rate of 200mL/min by a temperature raising rate program of 5 ℃/min, keeping the temperature for 10h, and naturally cooling the crucible to room temperature to prepare the white melamine-melamine adduct. 0.4g of the calcined adduct material of melamine and melem was then weighed out into an agate mortar in a glove box under nitrogen and mixed with 2.7g of lithium chloride and 3.3g of potassium chloride before intensive grinding. The milled mixture was then poured into a ceramic crucible and the lid was closed. And then, putting the crucible filled with the mixture into a tube furnace again, carrying out temperature programming to 560 ℃ at a temperature rise rate of 15 ℃/min under an argon atmosphere with a flow rate of 200mL/min, keeping for 4h, and naturally cooling to room temperature to prepare the solid solution of the triazine/heptazine allotrope heterojunction carbon nitride, the lithium chloride and the potassium chloride. Then dispersing the obtained solid solution into deionized water at 100 ℃ under the standard atmospheric pressure, filtering and washing by using a filter membrane with the diameter of 0.22 mu m after full dispersion, and repeating the washing process for 15 times. Finally, the obtained solid is collected and dried at the temperature of 60 ℃ to obtain the triazine/heptazine allotrope heterojunction carbon nitride photocatalyst material.
Example 3
The preparation of the adduct of melamine and melem is carried out as follows: 8.0g of melamine was weighed into a 100mL ceramic crucible and the crucible lid was covered. And then placing the crucible into a tube furnace, raising the temperature to 430 ℃ in an argon atmosphere with the flow rate of 350mL/min by a temperature raising rate program of 5 ℃/min, keeping the temperature for 20h, and naturally cooling the crucible to room temperature to prepare the white melamine-melamine adduct. 1.0g of the calcined adduct material of melamine and melem was then weighed into an agate mortar in a glove box under nitrogen and mixed with 2.7g of lithium chloride and 3.3g of potassium chloride before intensive grinding. The milled mixture was then poured into a ceramic crucible and the lid was closed. And then, putting the crucible filled with the mixture into a tubular furnace again, carrying out temperature programming to 600 ℃ at the temperature rising rate of 20 ℃/min under the argon atmosphere with the flow rate of 400mL/min, keeping for 6h, and naturally cooling to room temperature to prepare the solid solution of the triazine/heptazine allotrope heterojunction carbon nitride, the lithium chloride and the potassium chloride. Then dispersing the obtained solid solution into deionized water at 100 ℃ under the standard atmospheric pressure, filtering and washing by using a filter membrane with the diameter of 0.22 mu m after full dispersion, and repeating the washing process for 20 times. Finally, the obtained solid is collected and dried at the temperature of 60 ℃ to obtain the triazine/heptazine allotrope heterojunction carbon nitride photocatalyst material.
Example 4
The preparation of the adduct of melamine and melem is carried out as follows: 6.0g of melamine was weighed into a 100mL ceramic crucible and the crucible lid was covered. Then the crucible is placed in a tube furnace, the temperature is programmed to 370 ℃ at the heating rate of 8 ℃/min under the argon atmosphere with the flow rate of 100mL/min, the mixture is kept for 16h and then is naturally cooled to the room temperature to prepare the white melamine and melem adduct. 0.8g of the calcined adduct material of melamine and melem was then weighed out into an agate mortar in a glove box under nitrogen and mixed with 2.7g of lithium chloride and 3.3g of potassium chloride before intensive grinding. The milled mixture was then poured into a ceramic crucible and the lid was closed. And then, putting the crucible filled with the mixture into a tubular furnace again, carrying out temperature programming to 580 ℃ at a temperature rising rate of 15 ℃/min under an argon atmosphere with a flow rate of 100mL/min, keeping for 4h, and naturally cooling to room temperature to prepare the solid solution of the triazine/heptazine allotrope heterojunction carbon nitride, the lithium chloride and the potassium chloride. Then dispersing the obtained solid solution into deionized water at 100 ℃ under the standard atmospheric pressure, filtering and washing by using a filter membrane with the diameter of 0.22 mu m after full dispersion, and repeating the washing process for 18 times. Finally, the obtained solid is collected and dried at the temperature of 60 ℃ to obtain the triazine/heptazine allotrope heterojunction carbon nitride photocatalyst material which is named as 370-T/H-CN.
Example 5
The preparation of the adduct of melamine and melem is carried out as follows: 6.0g of melamine was weighed into a 100mL ceramic crucible and the crucible lid was covered. Then the crucible is placed in a tube furnace, the temperature is programmed to 390 ℃ at the heating rate of 8 ℃/min under the argon atmosphere with the flow rate of 100mL/min, the mixture is kept for 16h and then is naturally cooled to the room temperature to prepare the white melamine and melem adduct. 0.8g of the calcined adduct material of melamine and melem was then weighed out into an agate mortar in a glove box under nitrogen and mixed with 2.7g of lithium chloride and 3.3g of potassium chloride before intensive grinding. The milled mixture was then poured into a ceramic crucible and the lid was closed. And then, putting the crucible filled with the mixture into a tubular furnace again, carrying out temperature programming to 580 ℃ at a temperature rising rate of 15 ℃/min under an argon atmosphere with a flow rate of 100mL/min, keeping for 4h, and naturally cooling to room temperature to prepare the solid solution of the triazine/heptazine allotrope heterojunction carbon nitride, the lithium chloride and the potassium chloride. Then dispersing the obtained solid solution into deionized water at 100 ℃ under the standard atmospheric pressure, filtering and washing by using a filter membrane with the diameter of 0.22 mu m after full dispersion, and repeating the washing process for 18 times. Finally, the obtained solid is collected and dried at the temperature of 60 ℃ to obtain the triazine/heptazine allotrope heterojunction carbon nitride photocatalyst material which is named as 390-T/H-CN.
Example 6
The preparation of the adduct of melamine and melem is carried out as follows: 6.0g of melamine was weighed into a 100mL ceramic crucible and the crucible lid was covered. Then the crucible is placed in a tube furnace, the temperature is programmed to 410 ℃ at the heating rate of 8 ℃/min under the argon atmosphere with the flow rate of 100mL/min, the mixture is kept for 16h and then is naturally cooled to the room temperature to prepare the white melamine and melem adduct. 0.8g of the calcined adduct material of melamine and melem was then weighed out into an agate mortar in a glove box under nitrogen and mixed with 2.7g of lithium chloride and 3.3g of potassium chloride before intensive grinding. The milled mixture was then poured into a ceramic crucible and the lid was closed. And then, putting the crucible filled with the mixture into a tubular furnace again, carrying out temperature programming to 580 ℃ at a temperature rising rate of 15 ℃/min under an argon atmosphere with a flow rate of 100mL/min, keeping for 4h, and naturally cooling to room temperature to prepare the solid solution of the triazine/heptazine allotrope heterojunction carbon nitride, the lithium chloride and the potassium chloride. Then dispersing the obtained solid solution into deionized water at 100 ℃ under the standard atmospheric pressure, filtering and washing by using a filter membrane with the diameter of 0.22 mu m after full dispersion, and repeating the washing process for 18 times. Finally, the obtained solid is collected and dried at the temperature of 60 ℃ to obtain the triazine/heptazine allotrope heterojunction carbon nitride photocatalyst material which is named as 410-T/H-CN.
Example 7
The preparation of the adduct of melamine and melem is carried out as follows: 6.0g of melamine was weighed into a 100mL ceramic crucible and the crucible lid was covered. Then the crucible is placed in a tube furnace, the temperature is programmed to 420 ℃ at the heating rate of 8 ℃/min under the argon atmosphere with the flow rate of 100mL/min, the mixture is kept for 16h and then is naturally cooled to the room temperature to prepare the white melamine and melem adduct. 0.8g of the calcined adduct material of melamine and melem was then weighed out into an agate mortar in a glove box under nitrogen and mixed with 2.7g of lithium chloride and 3.3g of potassium chloride before intensive grinding. The milled mixture was then poured into a ceramic crucible and the lid was closed. And then, putting the crucible filled with the mixture into a tubular furnace again, carrying out temperature programming to 580 ℃ at a temperature rising rate of 15 ℃/min under an argon atmosphere with a flow rate of 100mL/min, keeping for 4h, and naturally cooling to room temperature to prepare the solid solution of the triazine/heptazine allotrope heterojunction carbon nitride, the lithium chloride and the potassium chloride. Then dispersing the obtained solid solution into deionized water at 100 ℃ under the standard atmospheric pressure, filtering and washing by using a filter membrane with the diameter of 0.22 mu m after full dispersion, and repeating the washing process for 18 times. Finally, the obtained solid is collected and dried at the temperature of 60 ℃ to obtain the triazine/heptazine allotrope heterojunction carbon nitride photocatalyst material which is named as 420-T/H-CN.
Example 8
The preparation of the adduct of melamine and melem is carried out as follows: 6.0g of melamine was weighed into a 100mL ceramic crucible and the crucible lid was covered. Then the crucible is placed in a tube furnace, the temperature is programmed to 430 ℃ at the heating rate of 8 ℃/min under the argon atmosphere with the flow rate of 100mL/min, the mixture is kept for 16h and then is naturally cooled to the room temperature to prepare the white melamine and melem adduct. 0.8g of the calcined adduct material of melamine and melem was then weighed out into an agate mortar in a glove box under nitrogen and mixed with 2.7g of lithium chloride and 3.3g of potassium chloride before intensive grinding. The milled mixture was then poured into a ceramic crucible and the lid was closed. And then, putting the crucible filled with the mixture into a tubular furnace again, carrying out temperature programming to 580 ℃ at a temperature rising rate of 15 ℃/min under an argon atmosphere with a flow rate of 100mL/min, keeping for 4h, and naturally cooling to room temperature to prepare the solid solution of the triazine/heptazine allotrope heterojunction carbon nitride, the lithium chloride and the potassium chloride. Then dispersing the obtained solid solution into deionized water at 100 ℃ under the standard atmospheric pressure, filtering and washing by using a filter membrane with the diameter of 0.22 mu m after full dispersion, and repeating the washing process for 18 times. Finally, the obtained solid is collected and dried at the temperature of 60 ℃ to obtain the triazine/heptazine allotrope heterojunction carbon nitride photocatalyst material which is named as 430-T/H-CN.
Example 9
The preparation of the adduct of melamine and melem is carried out as follows: 6.0g of melamine was weighed into a 100mL ceramic crucible and the crucible lid was covered. Then the crucible is placed in a tube furnace, the temperature is programmed to 450 ℃ at the heating rate of 8 ℃/min under the argon atmosphere with the flow rate of 100mL/min, the mixture is kept for 16h and then is naturally cooled to the room temperature to prepare the white melamine and melem adduct. 0.8g of the calcined adduct material of melamine and melem was then weighed out into an agate mortar in a glove box under nitrogen and mixed with 2.7g of lithium chloride and 3.3g of potassium chloride before intensive grinding. The milled mixture was then poured into a ceramic crucible and the lid was closed. And then, putting the crucible filled with the mixture into a tubular furnace again, carrying out temperature programming to 580 ℃ at a temperature rising rate of 15 ℃/min under an argon atmosphere with a flow rate of 100mL/min, keeping for 4h, and naturally cooling to room temperature to prepare the solid solution of the triazine/heptazine allotrope heterojunction carbon nitride, the lithium chloride and the potassium chloride. Then dispersing the obtained solid solution into deionized water at 100 ℃ under the standard atmospheric pressure, filtering and washing by using a filter membrane with the diameter of 0.22 mu m after full dispersion, and repeating the washing process for 18 times. Finally, the obtained solid is collected and dried at the temperature of 60 ℃ to obtain the triazine/heptazine allotrope heterojunction carbon nitride photocatalyst material which is named as 450-T/H-CN.
XRD, TEM and DRS characteristics of the catalyst are shown in figures 1, 2 and 3.
FIG. 1: the XRD analysis shows that the carbon nitride has two crystal structures, and the peak of the triazine crystal form gradually disappears along with the increase of the temperature. When the temperature in the step (1) is up to 450 ℃, the triazine crystal form completely disappears.
FIG. 2: SEM analysis shows that the prepared triazine/heptazine allotrope heterojunction carbon nitride has a rod-shaped cluster structure.
FIG. 3: through DRS analysis, it was found that the absorption of light by carbon nitride was somewhat red-shifted with increasing temperature.
FIG. 4: the hydrogen activity diagram for the water photocatalytic decomposition of triazine/heptazine homone heterojunction carbon nitride photocatalyst can be found, and the diagram is compared with the block g-C3N4The hydrogen production activity of the porous carbon nitride is obviously improved, wherein g-C3N4The hydrogen production amounts of 370-T/H-CN, 390-T/H-CN, 410-T/H-CN, 430-T/H-CN and 450-T/H-CN were 9.3. mu. mol/H, 342.4. mu. mol/H, 382.9. mu. mol/H, 657.7. mu. mol/H, 607.2. mu. mol/H and 486.1. mu. mol/H, respectively. The triazine/heptazine allotrope heterojunction carbon nitride obtained at the temperature of 410 ℃ has the highest hydrogen production activity, when the dosage of the catalyst is 0.02g, the hydrogen production activity can reach 657.7 mu mol/h, about 32885 mu mol/gh, and the quantum efficiency can reach as high as57％。
Claims (9)
1. A preparation method of a triazine/heptazine homone heterojunction carbon nitride photocatalyst is characterized by comprising the following specific preparation steps:
(1) preparation of melamine and melem adducts: weighing melamine, placing the melamine in a ceramic crucible, and covering the crucible with a cover; then placing the crucible in a tube furnace, under the protection of high-purity argon, raising the temperature to a certain temperature at a certain heating rate program, keeping the temperature for a period of time, and naturally cooling the crucible to room temperature to obtain a white melamine and melem adduct;
(2) uniformly grinding the mixture of the melamine and miller amine adduct obtained in the step (1) and lithium chloride and potassium chloride in a glove box under the protection of nitrogen, pouring the mixture into a ceramic crucible, and covering the ceramic crucible with a cover;
(3) placing the ceramic crucible in a tube furnace, heating to a certain temperature at a certain heating rate under the protection of argon atmosphere, keeping for a period of time, and naturally cooling to room temperature to obtain a solid solution of triazine/heptazine allotrope heterojunction carbon nitride, lithium chloride and potassium chloride;
(4) and (4) dispersing the solid solution obtained in the step (3) by using boiling water, and filtering and washing to obtain the triazine/heptazine allotrope heterojunction carbon nitride photocatalyst.
2. The method for preparing a triazine/heptazine homone heterojunction carbon nitride photocatalyst as claimed in claim 1, wherein in the step (1), the temperature rise rate is 2-10 ℃/min; the temperature rise is 360-430 ℃, and the holding time is 4-24 h; the flow rate of the argon is 50-400 mL/min.
3. The method for preparing a triazine/heptazine homone heterojunction carbon nitride photocatalyst as claimed in claim 1, wherein in the step (2), the mass ratio of the adduct of melamine and melem to the mixture of lithium chloride and potassium chloride is 1:30-1: 6; in the mixture of lithium chloride and potassium chloride, the mass ratio of lithium chloride to potassium chloride is 9: 11.
4. The method for preparing a triazine/heptazine homone heterojunction carbon nitride photocatalyst as claimed in claim 1, wherein in the step (3), the temperature rise rate is 10-20 ℃/min; the temperature rise is 550-600 ℃, and the holding time is 4-6 h; the flow rate of the argon is 50-400 mL/min.
5. The method for preparing a triazine/heptazine homone heterojunction carbon nitride photocatalyst as claimed in claim 1, wherein in the step (4), the boiling water is deionized water with 100 ℃ under standard atmospheric pressure; the filtration washing is filtration washing by a filter membrane with the diameter of 0.22 mu m; the number of washing times is 6-20.
6. The method for preparing a triazine/heptazine homone heterojunction carbon nitride photocatalyst as claimed in claim 2, wherein in the step (1), the temperature rise rate is 8 ℃/min; the temperature rise is 410 ℃, and the holding time is 16 h; the flow rate of the argon is 100 mL/min.
7. The method for preparing the triazine/heptazine homone heterojunction carbon nitride photocatalyst as claimed in claim 3, wherein the mass ratio of the adduct of melamine and melem to the mixture of lithium chloride and potassium chloride is 1: 7.5.
8. The method for preparing a triazine/heptazine homone heterojunction carbon nitride photocatalyst as claimed in claim 4, wherein in the step (3), the temperature rise rate is 15 ℃/min; the temperature rise is 580 ℃, and the holding time is 4 h; the flow rate of the argon is 100 mL/min.
9. Use of the triazine/heptazine homone heterojunction carbon nitride photocatalyst prepared by the method as claimed in any one of claims 1 to 8, wherein the hydrogen is produced by photocatalytic decomposition of water under irradiation of visible light.
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